Supporting Information

Keteniminium Salts: Reactivity and Propensity towards

Electrocyclization Reactions
Gamze Tanriver,a Dylan Dagoneau,b Ulfet Karadeniz,a Amandine Kolleth,b Alexandre Lumbroso,b
Sarah Sulzer-Mossé,b Alain De Mesmaekerb and Saron Catak*a
a
Bogazici University, Department of Chemistry, Bebek 34342 Istanbul, Turkey
b
Syngenta Crop Protection AG, Crop Protection Research, Research Chemistry, Schaffhauserstrasse 101,

CH-4332, Switzerland

saron.catak@boun.edu.tr

Electronic Supporting Information

Table of Contents
Full reference of Gaussian09......................................................................................................................... S2
DFT Survey..................................................................................................................................................... S2
Figure S1. The non-covalent interaction (NCI) plots of the optimized KI structures. .................................... S4
Table S2. Evolution of distances through the electrocyclization reaction (distances in Å). ........................... S5
Figure S2. Optimized TS structures (M06-2X/6-31+G(d,p) in CHCl3, 6-311++G(3df,3pd) extra basis set for
S atom). ............................................................................................................................................................ S6
Figure S3. Optimized intermediate structures (M06-2X/6-31+G(d,p) in CHCl3, 6-311++G(3df,3pd) extra
basis set for S atom). All energies in Figure S3 are relative to the pre-reactive conformer (PRC). ............... S7
Figure S4. Optimized end product structures (M06-2X/6-31+G(d,p) in CHCl3, 6-311++G(3df,3pd) extra
basis set for S atom). ........................................................................................................................................ S8
Frontier Molecular Orbitals (FMO) Analysis ............................................................................................. S9
Figure S5. HOMO of keteniminium ions. (M06-2X/6-311++G(d,p)//M06-2X/6-31+G(d,p) in CHCl3, extra
basis set for S atom; iso-surface value = 0.03 au). ........................................................................................... S9
Figure S6. One of the representative image of points (Bq ghost atoms) for NICS calculations ................... S10
Substituent effect tables of Groups I and II .............................................................................................. S11
Table S3. Gibbs free energy barriers for the formation of 3-aminopyrrole derivatives in Group I (energies in
kcal/mol at 298 K and 1 atm) ......................................................................................................................... S11
Table S4. Gibbs free energy barriers for the formation of 3-aminofuran derivatives in Group I (energies in
kcal/mol at 298 K and 1 atm) ......................................................................................................................... S12
Table S5. Gibbs free energy barriers for the formation of 3-aminothiophene derivatives in Group I (energies
in kcal/mol at 298 K and 1 atm) ..................................................................................................................... S13

S1
Table S6. Gibbs free energy barriers for the formation of 3-aminoindole derivatives in Group II (energies in
kcal/mol at 298 K and 1 atm) ......................................................................................................................... S14
Table S7. Gibbs free energy barriers for the formation of 3-aminobenzofuran derivatives in Group II
(energies in kcal/mol at 298 K and 1 atm) ..................................................................................................... S15
Table S8. Gibbs free energy barriers for the formation of 3-aminobenzothiophene derivatives in Group I
(energies in kcal/mol at 298 K and 1 atm) ..................................................................................................... S16
Effect of N-substituents on Keteniminium Reactivity .............................................................................. S17
Table S9. Effect of N-substituents on free energy barriers (ΔGǂ), and reaction free energies (∆Grxn) of 6π-
electrocyclizations of keteniminium salts in Groups I and II.a,b .................................................................... S17
Cartesian Coordinates for Keteniminiums (KI) ....................................................................................... S18
Cartesian Coordinates for TS structures ................................................................................................... S26
Cartesian coordinates for intermediates .................................................................................................... S33
Characterization of Compounds 11a, 13a, 14a and 15a - 1H and 13C NMR Spectra ............................. S40

Full reference of Gaussian09

Gaussian 09, Revision E.01,
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G.
Scalmani, V. Barone, B. Mennucci,G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian,
A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.
Hasegawa, M. Ishida, T. Nakajima,Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery,
Jr.,J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T.
Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi,
M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J.
Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg,
S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox,
Gaussian, Inc., Wallingford CT, 2013.

DFT Survey
Besides M06-2X functional, all calculation in Table S1 were also performed at the hybrid-GGA
B3LYP, hybrid-meta GGA MPWB1K and Second order Møller–Plesset perturbation (MP2). The
calculations indicate that even though B3LYP, MPWB1K and MP2 lower the barriers compared to
M06-2X optimizations, similar barrier trends were observed regardless of the level of theory.

S2
Table S1. Free energy barriers (ΔGǂ), and reaction free energies (∆Grxn) for 6π-
electrocyclization reactions of KIs.a,b

M06-2X/ B3LYP/ MPWB1K/ MP2/

6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p)
Group I ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn
1 pyrrole 3.0 -37.8 2.2 -36.1 1.5 -43.0 * -41.9
2 furan 6.0 -23.8 6.5 -20.5 5.5 -27.2 3.4 -22.9
3 thiophene 11.4 -22.2 10.6 -19.4 10.4 -26.8 8.2 -23.4
4 cyclohexadiene 9.2 -34.8 10.3 -28.6 10.5 -37.1 5.1 -36.6
Group II ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn
5 indole 10.8 -4.9 10.2 -3.2 8.8 -9.1 6.1 -7.3
6 benzofuran 17.0 8.0 15.4 8.5 14.8 3.0 13.6 8.7
7 benzothiophene 21.0 9.0 20.4 10.6 18.8 4.3 16.0 9.3
8 naphthalene 14.8 1.7 18.1 8.6 16.2 0.8 6.2 -0.4
a
M06-2X/6-31+G(d,p) in chloroform (ε=4.7113); free energies in kcal/mol.
b
6-311++G(3df,3pd) extra basis set for sulfur atom.
* The TS was not located at the MP2 level of theory.

S3
 Figure S1. The non-covalent interaction (NCI) plots of the optimized KI structures. NCI
isosurface values= 0.5 and 0.7 au using SCF densities. NCI color scale is -0.04 < ρ < 0.04
au.

S4
Table S2. Evolution of distances through the electrocyclization reaction (distances in Å).

Distance KIa KI-PRC TS Intb Distance KIa KI-PRC TS Intb

N1-C2 1.25 1.27 1.28 1.36 N1-C2 1.25 1.27 1.29 1.37
C2-C3 1.31 1.39 1.38 1.37 C2-C3 1.31 1.39 1.38 1.37
N-C3 1.42 1.34 1.35 1.44 N-C3 1.42 1.33 1.36 1.41
N-C4 1.42 1.43 1.39 1.30 N-C4 1.42 1.44 1.38 1.32
C4-C5 1.34 1.33 1.35 1.48 C4-C5 1.40 1.39 1.41 1.48
C2-C5 3.34 2.88 2.42 1.51 C2-C5 3.62 4.33 2.10 1.53

Distance KI TS Intb Distance KI TS Intb

N1-C2 1.25 1.28 1.36 N1-C2 1.25 1.30 1.37
C2-C3 1.32 1.34 1.36 C2-C3 1.32 1.35 1.36
O-C3 1.34 1.35 1.43 O-C3 1.35 1.36 1.40
O-C4 1.41 1.36 1.27 O-C4 1.40 1.35 1.31
C4-C5 1.33 1.36 1.48 C4-C5 1.39 1.41 1.46
C2-C5 3.11 2.19 1.51 C2-C5 3.22 1.98 1.54

Distance KI TS Intb Distance KI TS Intb

N1-C2 1.25 1.28 1.35 N1-C2 1.25 1.30 1.36
C2-C3 1.30 1.34 1.39 C2-C3 1.30 1.35 1.37
S-C3 1.76 1.73 1.72 S-C3 1.77 1.73 1.73
S-C4 1.79 1.73 1.62 S-C4 1.78 1.73 1.67
C4-C5 1.33 1.36 1.49 C4-C5 1.40 1.41 1.47
C2-C5 3.54 2.22 1.51 C2-C5 3.30 2.01 1.54
a
KI (Reactant) unless specified is linear.
b
Note that the electrocyclization initially leads to an intermediate (Int) where C5 bears a H atom.
Upon deprotonation of C5, aromaticity is established, and the end product is obtained.

S5
Figure S2. Optimized TS structures (M06-2X/6-31+G(d,p) in CHCl3, 6-311++G(3df,3pd) extra basis set for S atom).
All energies for the formation of pyrrole and indole derivatives in Figure S2 are relative to the pre-reactive conformer (PRC).

S6
Figure S3. Optimized intermediate structures (M06-2X/6-31+G(d,p) in CHCl3, 6-311++G(3df,3pd) extra basis set for S
atom).

S7
Figure S4. Optimized end product structures (M06-2X/6-31+G(d,p) in CHCl3, 6-311++G(3df,3pd) extra basis set for S
atom).

S8
Frontier Molecular Orbitals (FMO) Analysis

According to Woodward-Hoffmann rules,1 pericyclic ring closure in (4n+2) systems proceeds through a concerted
disrotatory motion. FMO analysis of the keteniminiums in Groups I and II (Figure 5) show HOMOs of keteniminiums
primed for a disrotatory closure.

Figure S5. HOMO of keteniminium ions. (M06-2X/6-311++G(d,p)//M06-2X/6-31+G(d,p) in CHCl3, extra basis set for
S atom; iso-surface value = 0.03 au).

S9
Figure S6. One of the representative image of points (Bq ghost atoms) for NICS calculations

S10
Substituent effect tables of Groups I and II
In general, in case of energy refinements with MPW1K and B2LYP, the activation barriers of phenyl substituent (entry 5,
Group I) decrease sharply compared to the M06-2X and ωB97XD.

Table S3. Gibbs free energy barriers for the formation of 3-aminopyrrole derivatives in Group I (energies in
kcal/mol at 298 K and 1 atm)

M06-2X/ MPW1K/ ωB97XD/ B2PLYP/

6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p)

Entry R1 R2 ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn

1 CH3 H 3.0 -37.8 1.9 -42.4 2.9 -39.3 4.8 -34.3
2(E) H CH3 (E) 2.8 -29.8 2.9 -31.2 2.3 -30.9 6.4 -22.3
3(Z) H CH3 (Z) 7.0 -33.0 8.6 -36.0 8.0 -33.5 13.7 -27.2
4 H H 2.9 -35.1 2.1 -39.0 2.7 -36.3 5.0 -30.9
5 Ph H 3.8 -35.0 0.6 -42.0 3.7 -36.5 2.7 -34.6
6(E) H Ph 2.6 -30.6 1.9 -30.6 2.3 -32.0 4.6 -22.1
7(Z) H Ph 5.4 -31.1 5.9 -36.7 6.4 -31.7 10.7 -29.3
8 CO2Me H 6.4 -31.8 6.2 -36.7 6.8 -33.6 10.6 -26.3
9(E) H CO2Me 6.0 -24.7 6.7 -25.3 4.7 -26.4 10.0 -16.8
10 CO2Me CO2Me 7.2 -26.7 6.4 -29.1 7.4 -27.5 10.5 -18.7
11 CN H 5.3 -32.4 5.4 -36.8 5.0 -34.3 9.8 -26.1
12(E) H CN (E) 7.0 -19.3 7.6 -19.6 5.9 -20.8 14.3 -11.1
13(Z) H CN (Z) 8.0 -22.9 10.7 -24.6 8.3 -24.6 15.5 -16.9

S11
Table S4. Gibbs free energy barriers for the formation of 3-aminofuran derivatives in Group I (energies in kcal/mol
at 298 K and 1 atm)

M06-2X/ MPW1K/ ωB97XD/ B2PLYP/

6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p)

Entry R1 R2 ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn

1 CH3 H 6.0 -23.8 4.8 -27.8 5.5 -26.6 10.1 -19.1
2(E) H CH3 (E) 10.6 -14.0 11.0 -15.7 9.9 -16.0 17.6 -6.8
3(Z) H CH3 (Z) 15.6 -14.1 17.2 -16.0 15.7 -16.1 24.0 -6.9
4 H H 10.5 -16.1 10.5 -18.6 10.0 -18.4 16.8 -8.9
5 Ph H 8.3 -23.9 4.1 -31.3 8.0 -26.7 7.5 -24.2
6(E) H Ph 9.4 -13.4 10.1 -12.7 8.4 -16.4 16.5 -2.4
7(Z) H Ph 15.1 -11.5 15.6 -16.1 14.6 -14.1 22.6 -8.1
8 CO2Me H 12.8 -12.7 10.9 -18.3 11.8 -16.3 17.0 -7.7
9(E) H CO2Me 12.6 -8.3 13.3 -8.7 11.9 -9.8 19.7 1.3
10 CO2Me CO2Me 16.9 -6.5 15.1 -9.3 15.1 -9.9 21.5 2.0
11 CN H 15.9 -9.3 14.3 -14.6 14.7 -12.9 20.4 -3.7
12(E) H CN (E) 15.3 -1.7 15.7 -2.8 14.6 -3.5 22.5 6.5
13(Z) H CN (Z) 20.1 -1.0 22.5 -2.8 20.3 -2.9 30.5 7.6

S12
Table S5. Gibbs free energy barriers for the formation of 3-aminothiophene derivatives in Group I (energies in kcal/mol
at 298 K and 1 atm)

M06-2X/ MPW1K/ ωB97XD/ B2PLYP/

Yield%2
6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p)

Entry R1 R2 ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn

1 CH3 H 11.4 -22.2 9.9 -27.4 10.9 -25.0 15.5 -16.9 80%
2(E) H CH3 (E) 14.5 -14.5 15.1 -15.8 13.8 -15.9 21.7 -4.8
3(Z) H CH3 (Z) 20.2 -15.0 22.3 -17.7 20.5 -17.0 29.2 -7.1
4 H H 14.3 -18.5 14.4 -22.0 13.9 -20.9 20.6 -10.8
5 Ph H 13.5 -22.1 9.4 -30.0 13.4 -24.4 13.3 -20.9 95%
72%
6(E) H Ph 13.1 -13.8 14.0 -13.5 12.4 -16.1 20.5 -1.5
E/Z:80:20
10%
7(Z) H Ph 18.7 -14.0 19.8 -19.2 18.6 -16.5 27.0 -9.8
E/Z 13:87
8 CO2Me H 15.7 -18.0 13.8 -24.5 14.6 -21.4 19.8 -13.1 47%
56%
9(E) H CO2Me 15.4 -10.7 17.4 -11.0 14.7 -12.3 23.9 0.4
E/Z:60:40
58%
10 CO2Me CO2Me 17.0 -13.5 15.6 -17.1 15.9 -15.5 21.5 -5.3
E/Z:67:33
11 CN H 20.0 -14.0 19.4 -19.1 19.5 -16.6 25.7 -7.3 36%
12(E) H CN (E) 16.1 -6.7 16.9 -7.9 15.7 -8.2 23.6 3.5 54%
13(Z) H CN (Z) 21.1 -7.1 23.5 -9.1 21.4 -9.0 31.4 1.5 E/Z:100:0

S13
 Table S6. Gibbs free energy barriers for the formation of 3-aminoindole derivatives in Group II (energies in kcal/mol at 298
K and 1 atm)

M06-2X/ MPW1K/ ωB97XD/ B2PLYP/

Yield%
6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p)

Entry R1 (o-) R2 (m-) R3 (p-) R4 (m-) ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn
1 H H H H 10.8 -4.9 10.1 -8.3 11.6 -5.8 16.4 0.5 84%3
2 H CH3 H CH3 9.2 -4.7 9.2 -7.5 9.7 -6.2 15.1 1.5
3 CH3 H H H 15.2 -1.9 14.1 -5.9 16.0 -2.8 20.5 3.0
4 H CH3 H H 8.9 -7.5 8.1 -11.0 9.7 -8.4 14.1 -2.5
5 H H CH3 H 10.4 -4.9 9.7 -8.3 11.1 -5.8 16.0 0.5
6 H H CF3 H 10.1 -3.8 9.6 -7.1 10.7 -4.9 15.8 1.8
7 H CF3 H H 9.6 -3.5 9.1 -6.8 10.4 -4.3 15.6 2.7
8 CF3 H H H 17.2 1.5 15.8 -2.8 18.0 0.6 22.4 6.6
9 H H CN H 9.9 -3.9 9.2 -7.1 10.4 -5.0 15.6 1.9
10 H CN H H 10.5 -3.1 10.2 -6.3 11.4 -3.8 16.7 3.6
11 H Cl H H 10.0 -6.0 9.3 -9.3 10.8 -6.9 15.6 -0.3
12 H H Cl H 11.0 -4.1 10.4 -7.3 11.7 -5.1 16.8 1.6
13 Cl H Cl H 17.8 2.8 16.7 -0.9 18.0 1.5 23.2 8.4

S14
 Table S7. Gibbs free energy barriers for the formation of 3-aminobenzofuran derivatives in Group II (energies in kcal/mol at
298 K and 1 atm)

M06-2X/ MPW1K/ ωB97XD/ B2PLYP/ Yield%3

6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p)

Entry R1 (o-) R2 (m-) R3 (p-) R4 (m-) ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn
1 H H H H 17.0 8.0 15.5 4.2 16.1 5.3 22.4 12.7 69%
2 H CH3 H CH3 13.6 4.8 12.5 1.2 12.5 1.6 18.9 9.2 93%
3 CH3 H H H 16.3 6.3 14.0 1.7 15.4 3.6 20.6 9.9
4 H CH3 H H 14.6 4.4 12.9 0.4 13.8 1.8 19.4 8.4
5 H H CH3 H 16.6 7.0 15.0 3.3 15.7 4.3 21.9 11.8
6 H H CF3 H 18.1 9.6 16.3 5.7 17.0 6.9 23.5 14.5
7 H CF3 H H 19.6 11.7 18.0 7.9 18.7 9.3 25.5 17.5
8 CF3 H H H 18.9 11.9 16.0 6.7 17.3 8.6 23.2 15.6
9 H H CN H 19.3 12.2 17.6 8.7 18.2 9.6 25.1 17.6
10 H CN H H 19.8 12.0 18.5 8.5 19.0 9.7 26.2 18.5
11 H Cl H H 18.5 9.3 16.7 5.3 17.7 6.9 23.8 14.2
12 H H Cl H 17.5 10.1 15.7 6.3 16.4 7.5 23.0 15.1
13 Cl H Cl H 20.5 13.3 17.9 8.6 19.0 10.3 25.1 17.6 91%

S15
 Table S8. Gibbs free energy barriers for the formation of 3-aminobenzothiophene derivatives in Group I (energies in
kcal/mol at 298 K and 1 atm)

M06-2X/ MPW1K/ ωB97XD/ B2PLYP/ Yield% 4

6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p) 6-31+G(d,p)

Entry R1 (o-) R2 (m-) R3 (p-) R4 (m-) ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn
1 H H H H 21.0 9.0 18.6 3.9 20.4 6.9 25.5 13.8 93%
2 H CH3 H CH3 18.8 8.5 16.4 3.7 18.1 6.1 22.7 13.0 78%
3 CH3 H H H 19.3 7.6 15.9 1.4 18.9 5.6 22.2 10.7
4 H CH3 H H 18.9 7.1 15.9 1.2 18.5 4.9 22.2 10.5
5 H H CH3 H 21.7 10.4 17.2 3.2 21.2 8.3 25.8 14.9
6 H H CF3 H 22.8 11.5 20.0 6.0 22.3 9.5 26.9 16.0 80%
7 H CF3 H H 20.7 11.5 18.3 6.5 20.5 9.9 25.8 17.2
8 CF3 H H H 21.5 10.8 18.1 4.6 20.7 8.3 25.2 14.6 88%
9 H H CN H 22.0 12.3 20.1 7.9 21.5 10.3 27.7 18.4 47%
10 H CN H H 22.4 12.0 20.4 7.2 22.2 10.4 27.9 18.1
11 H Cl H H 21.2 9.3 17.6 3.0 20.7 7.3 25.1 13.7
12 H H Cl H 22.1 11.7 19.7 6.6 21.6 9.6 26.9 16.7
13 Cl H Cl H 22.9 13.0 19.8 7.3 21.9 10.5 26.8 17.3 89%

S16
Effect of N-substituents on Keteniminium Reactivity

The effect of N-substituents were investigated for the electrocyclization of Groups I and
II keteniminiums with the substitution pattern (Table S9).

Table S9. Effect of N-substituents on free energy barriers (ΔGǂ), and reaction free
energies (∆Grxn) of 6π-electrocyclizations of keteniminium salts in Groups I and II.a,b

Group I Pyrrole Furan Thiophene

ΔGǂ ΔGrxn ΔGǂ ΔGrxn ΔGǂ ΔGrxn

3.0 -37.8 6.0 -23.8 11.4 -22.2

2.8 -40.8 7.0 -27.0 11.9 -25.8

Group II Aniline Phenyl ether Phenyl sulfide

10.8 -4.9 17.0 8.0 21.0 9.0

10.3 -5.9 16.2 7.1 19.7 8.8

a
M06-2X/6-31+G(d,p) in CHCl3 (ε=4.7113); free energies in kcal/mol
b
6-311++G(3df,3pd) extra basis set for sulfur atom

S17
Cartesian Coordinates for Keteniminiums (KI)
Enamine 1 (reactant, linear)
C 2.570999 0.676045 0.097825
C 2.119135 1.578104 0.982986
H 2.649732 2.513553 1.104794
H 1.236593 1.422882 1.592740
C 0.768103 -0.844280 0.606572
C -0.383704 -0.453835 0.124117
C 0.902185 -1.574305 1.914404
H -0.051718 -1.645779 2.437556
H 1.623780 -1.039441 2.538573
H 1.282770 -2.583419 1.733819
N -1.459188 0.000264 -0.324541
C -1.943753 1.375045 0.008760
H -1.193576 1.838267 0.649698
H -1.990640 1.913521 -0.942641
C -2.367508 -0.802557 -1.197418
H -1.896970 -1.772810 -1.353074
H -2.419630 -0.263459 -2.148532
C -3.736590 -0.900194 -0.533515
H -3.648204 -1.497578 0.381200
H -4.399276 -1.440895 -1.214363
C -3.315717 1.272827 0.665840
H -3.208775 0.787898 1.643086
H -3.676292 2.289546 0.842893
C -4.293595 0.487273 -0.210170
H -5.254961 0.392132 0.300276
H -4.476872 1.035495 -1.142619
N 1.903820 -0.540727 -0.193005
C 2.707647 -1.722778 -0.531534
H 3.314494 -1.509393 -1.410673
H 2.031247 -2.541011 -0.783493
H 3.362647 -2.034633 0.291872
C 3.817343 0.911315 -0.711557
H 4.183283 1.921812 -0.530807
H 4.610739 0.208391 -0.440808
H 3.616352 0.796082 -1.781162

Energy = -578.660765 hartree

Enamine 1 (PRC, KI-1)
H -4.61329400 -1.06036900 -0.02822600
C -3.68976700 -1.47587300 -0.44121800
H -3.64881700 -1.21500200 -1.50337500
S18
H -3.73603900 -2.56060600 -0.34426300
C -2.47771800 -0.95596100 0.27685200
C -1.63535700 -1.70920700 0.98766900
H -1.78643200 -2.78009900 1.05192700
H -0.81351100 -1.27911300 1.54954700
C -1.01076100 0.85400500 -0.27177100
C -0.00641900 -0.01204400 -0.67450900
C -0.74237100 2.31441300 -0.52460600
H 0.27214100 2.45025900 -0.89887200
H -1.44106500 2.72508000 -1.25737700
H -0.85087000 2.86541400 0.41465400
N 1.12431900 -0.34475900 -0.19403600
C 2.09257500 -1.14538700 -0.98071500
H 1.63368400 -1.34269100 -1.94873800
H 2.22953200 -2.09219800 -0.44563300
C 1.60363200 0.00093500 1.17054600
H 0.82119500 0.58403800 1.66025600
H 1.73649600 -0.94496500 1.70920200
C 2.92515200 0.76125200 1.08227000
H 2.74726400 1.73381200 0.60810500
H 3.27596600 0.95388200 2.09996500
C 3.41326200 -0.39027900 -1.09740000
H 3.25018900 0.51973300 -1.68756800
H 4.11992800 -1.01528200 -1.64998300
C 3.96237900 -0.03024500 0.28375100
H 4.88184400 0.55247600 0.18501500
H 4.21952200 -0.94864900 0.82691900
N -2.22265400 0.44342800 0.10958400
C -3.37186700 1.35697700 0.14647500
H -4.07282200 0.99844200 0.89857300
H -3.04628400 2.35375400 0.43507100
H -3.86671700 1.39989000 -0.82810000

Energy = -578.673130 hartree

Enol Ether 2 (KI-2)

H -3.10562500 -2.47906200 -0.96849400
C -3.06281400 -1.39505200 -1.07675200
H -2.34545600 -1.14269300 -1.86506500
H -4.04466300 -1.02725800 -1.38809000
C -2.66773300 -0.75738100 0.21317100
C -2.40382700 -1.32924400 1.38187700
H -2.45599700 -2.40659900 1.48248800
H -2.15160000 -0.73392000 2.25321300
C -1.39362400 1.18749000 -0.04122500
C -0.28792700 0.46893900 -0.01965300
C -1.37590700 2.66637200 -0.26580100
H -1.84862000 3.15253100 0.59093300
S19
H -1.95389300 2.89296700 -1.16445800
H -0.35829100 3.03858200 -0.38109300
N 0.80198600 -0.14362500 0.03817900
C 1.44579100 -0.75465900 -1.16156400
H 0.78652000 -0.57212800 -2.00981300
H 1.49753500 -1.82972100 -0.96055400
C 1.56648400 -0.30346800 1.31039200
H 0.98809800 0.17894400 2.09777800
C 2.83745400 -0.15630100 -1.34006300
H 3.31051200 -0.65420500 -2.19058100
H 2.73946800 0.90533100 -1.59478400
H 1.61548400 -1.38112500 1.49779600
C 2.95926000 0.29378100 1.13382900
H 3.51913000 0.11684200 2.05601300
H 2.86940200 1.37903800 1.00838600
C 3.67409400 -0.32233300 -0.07019000
H 3.85140000 -1.38899400 0.11518900
H 4.65127800 0.14778400 -0.20371300
O -2.61576100 0.65252500 0.12168300

Energy = -559.269379 hartree

Vinyl sulfide 3 (KI-3)

H -1.33630500 -1.19286400 -1.82778500
C -2.04801200 -1.78624200 -1.24456400
H -1.66500300 -2.80481000 -1.15016800
H -2.98273800 -1.81127800 -1.81240500
C -2.28236600 -1.18421600 0.11273200
C -2.22341800 -1.84255300 1.27116700
H -1.97858300 -2.90160700 1.28598300
H -2.42964500 -1.35371900 2.21731300
S -2.77121400 0.53546900 0.13979400
C -1.21743300 1.33691400 -0.07781400
C -0.10283900 0.66192100 -0.04600500
C -1.25656300 2.83195800 -0.28193900
H -1.77701000 3.29441500 0.55983700
H -0.25079800 3.24478500 -0.35521300
H -1.80780500 3.05184700 -1.19862300
N 0.95419100 -0.00721100 0.02766500
C 1.65613400 -0.24325900 1.32555000
H 1.06611500 0.23761200 2.10512300
H 1.64700300 -1.32803500 1.47534300
C 1.62386700 -0.59888600 -1.16864400
H 1.02311700 -0.34136100 -2.04071200
C 3.08023600 0.29286200 1.23214700
H 3.58848900 0.05996000 2.17164000
H 3.04668100 1.38463000 1.13923200
H 1.60835800 -1.68338900 -1.01761200
S20
C 3.05130600 -0.06842400 -1.25791500
H 3.53813300 -0.56080600 -2.10387000
H 3.01899400 1.00478800 -1.47757900
C 3.81837100 -0.31998600 0.04107500
H 3.93201100 -1.39991100 0.19723100
H 4.82337400 0.10219200 -0.03282400

Energy = -882.282789 hartree

Butadiene 4
H 5.24148100 -2.22057300 0.02109100
C 4.23843900 -1.79149000 0.00952400
H 3.71826800 -2.15793800 -0.88175900
H 3.69590600 -2.16358500 0.88500400
C 4.30330100 -0.28794300 0.01443300
C 5.46591500 0.38246200 0.03942200
H 5.49114000 1.46826300 0.04370700
H 6.41816600 -0.13796300 0.05800700
C 0.60278000 0.73693400 -0.03664700
C -0.57228800 0.15958800 -0.02274000
C 0.65458300 2.24976700 -0.07616400
H 1.19542500 2.56968200 -0.96976200
H 1.18501400 2.61451300 0.80650200
H -0.34427900 2.68504000 -0.09219200
N -1.70499200 -0.37211900 0.00525600
C -2.43732600 -0.62837600 1.28351000
H -1.77979700 -0.33284600 2.10043400
H -2.60905700 -1.70845000 1.32212600
C -2.45880900 -0.72963500 -1.23550200
H -1.81736500 -0.49786700 -2.08523400
C -3.75043000 0.14687000 1.26245100
H -4.29511700 -0.09155200 2.17999600
H -3.53056100 1.22120100 1.28143700
H -2.62516200 -1.81021600 -1.18553300
C -3.77592300 0.03909800 -1.25392100
H -4.33717400 -0.27980800 -2.13630100
H -3.56333800 1.10807900 -1.37062300
C -4.57821900 -0.20623300 0.02528700
H -4.87826500 -1.26050900 0.07413800
H -5.49497000 0.38796400 0.00867600
C 1.82458200 -0.07682900 -0.01441800
H 1.69757300 -1.15515900 -0.00238500
C 3.05168600 0.47396900 -0.00791300

S21
H 3.15731200 1.55747400 -0.01804900

Energy = -561.435580 hartree

Aniline 5 (reactant, linear)

H 2.774697 2.510887 -0.653685
C 2.824513 1.457365 -0.407104
C 3.016387 -1.245275 0.249332
C 1.658516 0.714943 -0.184845
C 4.072055 0.840055 -0.307317
C 4.179696 -0.507227 0.024319
C 1.766911 -0.646649 0.138873
H 0.868872 -1.238585 0.293139
C -0.601266 0.852721 0.617215
C -0.382541 0.983515 2.100773
H 0.511961 0.425314 2.387781
H -1.236016 0.612780 2.669064
H -0.220197 2.039449 2.336909
C -1.708611 0.365649 0.115397
N -2.776285 -0.064306 -0.373704
C -3.018174 -1.520907 -0.608996
H -3.189628 -1.625652 -1.684682
H -2.107821 -2.051710 -0.331210
C -3.926466 0.829747 -0.707644
H -4.097379 0.707434 -1.781701
H -3.616566 1.853821 -0.501551
C -4.236920 -1.955320 0.198702
H -4.433647 -3.005265 -0.033808
H -3.997637 -1.895588 1.266933
C -5.139790 0.394575 0.106713
H -5.983157 1.024990 -0.187051
H -4.943184 0.582864 1.168593
C -5.453524 -1.084880 -0.122355
H -5.749917 -1.237249 -1.167372
H -6.300137 -1.386357 0.498954
N 0.373637 1.295448 -0.318789
C 0.277302 2.713608 -0.670586
H 0.721096 3.365876 0.093404
H 0.784759 2.879544 -1.622528
H -0.774177 2.973335 -0.793136
H 4.965614 1.430137 -0.484696
H 3.079525 -2.298812 0.502658
H 5.153277 -0.978111 0.105022

S22
Energy = -692.943930 hartree

Aniline 5 (PRC, KI-4)

H 1.855709 -2.122386 0.449040
C 2.436653 -1.225240 0.256171
C 3.894562 1.107555 -0.238572
C 1.832462 0.026285 0.354392
C 3.782931 -1.303669 -0.094624
C 4.509526 -0.139752 -0.345783
C 2.550868 1.196736 0.119915
H 5.556826 -0.204547 -0.621203
H 2.064396 2.161891 0.226714
C -0.499731 0.504903 -0.091701
C -0.199121 0.774818 -1.539727
H 0.392787 1.685518 -1.654474
H -1.127846 0.892660 -2.099237
H 0.377037 -0.061308 -1.944244
C -1.761323 0.866641 0.370767
N -2.868572 0.240433 0.432432
C -4.115972 0.914330 0.867533
H -4.476515 0.378244 1.752579
H -3.850378 1.933829 1.144480
C -3.066675 -1.180874 0.038646
H -3.424441 -1.709510 0.929277
H -2.093205 -1.582343 -0.248337
C -5.145992 0.858268 -0.257394
H -6.066919 1.330021 0.095685
H -4.777885 1.450420 -1.103860
C -4.089801 -1.265098 -1.091809
H -4.250574 -2.320171 -1.330115
H -3.672095 -0.787066 -1.986044
C -5.401340 -0.584577 -0.695623
H -5.867677 -1.140314 0.127766
H -6.101758 -0.605789 -1.534407
N 0.449339 0.102931 0.745021
C 0.088329 -0.212763 2.129909
H -0.449144 -1.163087 2.183887
H 0.996564 -0.272888 2.726163
H -0.551385 0.589867 2.517618
H 4.261150 -2.273956 -0.175647
H 4.461432 2.013594 -0.424130

Energy = -692.959073 hartree

Phenyl Ether 6 (KI-5)

H 2.36304800 0.45905500 2.13054500
C 2.47849700 -0.10118200 1.20823600
C 2.77427900 -1.47739800 -1.21297000
S23
C 2.18376600 0.50120800 -0.00758300
C 2.93061300 -1.42082900 1.20132800
C 3.07534100 -2.10734900 -0.00454400
C 2.32270900 -0.15829700 -1.22276300
H 3.17479500 -1.90809200 2.13927700
H 3.43179300 -3.13183300 -0.00359700
H 2.09131400 0.35953500 -2.14845800
H 2.89834400 -2.00821500 -2.15089400
O 1.72860200 1.82924500 -0.00882100
C 0.38769700 1.96904400 -0.01354800
C -0.10295700 3.37959600 -0.07169800
H 0.28113700 3.92113600 0.79583400
H -1.19190600 3.42132100 -0.07447100
H 0.28431300 3.84704400 -0.97987000
C -0.42504300 0.93266900 0.04710800
N -1.23108600 -0.02451100 0.04533900
C -1.79790300 -0.60119000 1.30001800
H -1.47173000 -1.64577300 1.32589600
H -1.35484800 -0.05907000 2.13479500
C -1.72190900 -0.65898200 -1.21427200
H -1.39257400 -1.70250300 -1.17205900
H -1.22860600 -0.15332000 -2.04390400
C -3.31894900 -0.49217300 1.25162000
H -3.71768100 -0.96513400 2.15290200
H -3.60160200 0.56657300 1.28509500
C -3.24275200 -0.55338300 -1.26496400
H -3.58471000 -1.07156400 -2.16470000
H -3.52237900 0.50134800 -1.36833800
C -3.88016400 -1.15168000 -0.00957700
H -3.68469500 -2.23062200 0.02226600
H -4.96456300 -1.02260100 -0.04547000

Energy = -673.555742 hartree

Phenyl Sulfide 7 (KI-6)

H 1.50159300 -2.80876900 2.15408900
C 1.62944000 -2.27761000 1.21658200
C 1.97772400 -0.91475000 -1.20162900
C 1.50850300 -2.95632800 0.00313700
C 1.92073100 -0.91429600 1.22820900
C 2.08804400 -0.23892800 0.01649700
C 1.68670700 -2.27804400 -1.20341100
H 1.28475900 -4.01813400 -0.00191900
H 2.01554200 -0.37415000 2.16537700
H 1.60274200 -2.80924900 -2.14580800
H 2.11561400 -0.37451800 -2.13329400
C -0.26980800 1.21627000 -0.00911600
C 0.69961900 2.08728200 -0.01417800

S24
S 2.37288900 1.51659000 0.02118000
N -1.14758700 0.32259900 0.00332200
C -1.68476500 -0.29293200 -1.24610000
H -1.39510700 -1.34888500 -1.20259600
H -1.18248400 0.18626200 -2.08647300
C -1.72765600 -0.21183100 1.27098200
H -1.44026300 -1.26849800 1.30589300
H -1.25296800 0.32029300 2.09527300
C -3.20010500 -0.12756300 -1.27730600
H -3.57520000 -0.63755000 -2.16852700
H -3.44070600 0.93635100 -1.38289300
C -3.24292600 -0.04412600 1.23947600
H -3.48510400 1.02470100 1.26603000
H -3.64930700 -0.49409800 2.14916800
C -3.84321200 -0.69282600 -0.00943700
H -3.68639200 -1.77807400 0.02887600
H -4.92262300 -0.52487100 -0.03341200
C 0.49308000 3.57964100 -0.04797300
H 0.97660500 3.98835100 -0.93802200
H 0.95522900 4.02385700 0.83653300
H -0.56730100 3.82959500 -0.06483900

Energy = -996.571273 hartree

Styrene 8

C -3.488244 0.695453 -1.081901

C -4.022026 -0.493922 -0.559522
H -3.387292 -1.194660 -0.026375
C 0.286978 0.781969 -0.317136
C 1.191531 0.020371 0.245726
C 0.717110 2.126521 -0.863427
H 1.783617 2.294861 -0.716415
H 0.160615 2.918639 -0.357344
H 0.496952 2.168037 -1.932708
N 2.063494 -0.706803 0.772187
C 2.883463 -1.674882 -0.020021
H 2.539078 -1.623842 -1.052439
H 2.663288 -2.664450 0.392150
C 2.399367 -0.635541 2.227967
H 1.738983 0.105050 2.678119
C 4.357992 -1.321898 0.138259
H 4.941485 -2.069689 -0.405515
H 4.546184 -0.351018 -0.334784
H 2.173012 -1.625399 2.636697
C 3.876931 -0.293112 2.383551
S25
H 4.112214 -0.306283 3.451117
H 4.047080 0.727822 2.023354
C 4.757463 -1.279117 1.614090
H 4.655780 -2.280583 2.050617
H 5.807512 -0.992198 1.708072
C -1.102540 0.317033 -0.399800
H -1.308966 -0.665958 0.011097
C -2.072702 1.062933 -0.954837
H -1.816148 2.039233 -1.362255
C -4.344827 1.578817 -1.754414
H -3.943645 2.503588 -2.160521
C -5.697466 1.284630 -1.908266
H -6.345224 1.979579 -2.432476
C -5.371816 -0.786958 -0.712277
H -5.771380 -1.708759 -0.302060
C -6.214378 0.100193 -1.387511
H -7.267917 -0.132624 -1.503306

Energy = -675.718984 hartree

Cartesian Coordinates for TS structures

TS1 - transition state for the parent enamine molecule leading to pyrrole.
H 4.19338400 -0.96210500 1.18162300
C 3.94159200 -1.35465200 0.19281400
H 4.72580100 -1.05027600 -0.50684900
H 3.94247600 -2.44397900 0.23172600
C 2.59418300 -0.88210100 -0.26880800
C 1.62663100 -1.70349100 -0.73896100
H 1.77111500 -2.77682200 -0.71334300
H 0.82120700 -1.33260100 -1.36117300
C 0.05906500 -0.22000200 0.36546300
N -1.15582300 -0.38408600 -0.00506600
C -1.76428100 0.26509500 -1.19207400
H -1.02537000 0.95066700 -1.61010200
H -1.96416000 -0.52823900 -1.92331600
C -2.04471300 -1.34643400 0.68116800
H -1.49156400 -1.75078500 1.52845100
H -2.25242600 -2.15566500 -0.03011600
C -3.33723400 -0.65210400 1.10035200
H -3.10384300 0.10453000 1.85931200
H -3.99235400 -1.39276900 1.56703800
C -3.06018900 0.97023300 -0.79865600
H -2.82444200 1.80853300 -0.13188300
H -3.51176200 1.38875400 -1.70259900
C -4.01904600 0.00338800 -0.10151300

S26
H -4.92017500 0.53386600 0.21689400
H -4.33470700 -0.77287800 -0.81035600
N 2.28251900 0.46252900 -0.07095000
C 3.34312500 1.46403800 0.09353800
H 4.22495500 1.13674900 -0.45140200
H 3.59110700 1.59639000 1.15035000
H 3.01599600 2.41364800 -0.32682400
C 0.99361500 0.77606900 0.19336600
C 0.61631900 2.18785800 0.55086000
H 0.74404800 2.83307800 -0.32443200
H 1.23706800 2.57601500 1.36188800
H -0.42762000 2.22740300 0.86192900

Energy = -578.668366 hartree

Imaginary frequency= -218.6951 cm-1

TS2 - transition state for the parent enol ether molecule leading to furan.
H -4.37611200 -1.99412300 -0.00886000
C -4.18114000 -0.95425600 -0.26576100
H -4.22631700 -0.81957800 -1.35007400
H -4.95734900 -0.32514100 0.18083700
C -2.85767700 -0.52621900 0.25401700
C -1.88254700 -1.27203600 0.83162400
H -1.97920800 -2.35035700 0.86904300
H -1.23332300 -0.82021000 1.57868700
C -1.25890000 1.03731200 -0.17891100
C -0.38568900 0.01876500 -0.11114800
C -0.93751600 2.42356900 -0.62443500
H 0.10932300 2.49484600 -0.91934500
H -1.12412400 3.11877000 0.19874200
H -1.57511600 2.69946500 -1.46712800
N 0.85216900 -0.25366200 0.08578800
C 1.53838600 -1.30255000 -0.70039500
H 0.87746000 -1.58327500 -1.52062000
H 1.66759400 -2.16639900 -0.03557800
C 1.62158900 0.27932800 1.23550800
H 1.01852800 1.05810000 1.70475000
C 2.88916900 -0.78738800 -1.18694500
H 3.39670300 -1.59984500 -1.71398000
H 2.72336500 0.02043400 -1.90940000
H 1.75347700 -0.54833800 1.94440400
C 2.97613800 0.79832600 0.75998200
H 3.54296000 1.12148800 1.63751900
H 2.82167300 1.67942200 0.12575500
S27
C 3.73323000 -0.27975100 -0.01708200
H 3.97045900 -1.11595300 0.65314500
H 4.68289800 0.11918200 -0.38255000
O -2.57354200 0.77206900 -0.02057200

Energy = -559.259791 hartree

Imaginary frequency= -313.8585cm-1

TS3 - transition state for the parent vinyl sulfide molecule leading to thiophene.

H -3.90484300 -2.56348400 0.08455500

C -3.91737800 -1.52529500 -0.24748100
H -3.94952500 -1.49049500 -1.34030100
H -4.83166300 -1.05126200 0.12351200
C -2.71472000 -0.79738400 0.27099200
C -1.59494100 -1.36812800 0.78573700
H -1.47114600 -2.44688100 0.76785100
H -1.01157700 -0.83127200 1.53031900
S -2.69111300 0.91539900 0.00373300
C -0.98820600 1.12132400 -0.20393900
C -0.16314000 0.06758000 -0.11892800
C -0.49704000 2.47230200 -0.66192200
H -0.48033000 3.15974700 0.18866700
H -1.15396400 2.88328500 -1.43129600
H 0.51363300 2.39036600 -1.06482600
N 1.06031100 -0.25156800 0.09719100
C 1.71132600 -1.35807000 -0.63763200
H 1.03937700 -1.65783600 -1.44204700
H 1.81732300 -2.19252000 0.06763100
C 1.84656400 0.31537100 1.22030100
H 1.26553500 1.13290500 1.64983600
C 3.07492500 -0.90562200 -1.15088600
H 3.55849500 -1.75780800 -1.63609600
H 2.92954800 -0.13161800 -1.91359700
H 1.95484200 -0.47916900 1.97016300
C 3.21311500 0.77211900 0.71678900
H 3.79261100 1.12117000 1.57597700
H 3.07929900 1.62630400 0.04237900
C 3.93621000 -0.36338400 -0.00922700
H 4.15252200 -1.17195500 0.70066300
H 4.89519900 -0.00974100 -0.39628400

Energy = -882.264650 hartree

Imaginary frequency= -341.5195 cm-1

TS4 - transition state for the parent butadiene molecule leading to benzene
H 3.16867500 -2.87888600 0.44599300
S28
C 3.58494100 -1.87373800 0.52445600
H 3.62030400 -1.58095600 1.57819100
H 4.61736700 -1.89319000 0.16041800
C 2.78612600 -0.88505700 -0.27653200
C 1.64941500 -1.21026500 -0.94128500
H 1.24374400 -2.21763700 -0.90492600
H 1.26961700 -0.55403300 -1.72059900
C 0.95789700 1.43997500 0.19754100
C 0.20032400 0.35703000 0.04094500
C 0.32491000 2.61629300 0.91886600
H 0.37085800 3.48978500 0.26205800
H 0.88393100 2.84111300 1.83013000
H -0.71730100 2.42435000 1.17697600
N -0.94653800 -0.14288000 -0.18948500
C -1.41829200 -1.38509300 0.46704100
H -0.66204900 -1.68203200 1.19393700
H -1.48502300 -2.14973500 -0.31703500
C -1.86703500 0.41906200 -1.21342200
H -1.40831200 1.32797700 -1.60380300
C -2.78142900 -1.13539400 1.10524300
H -3.13356300 -2.07573600 1.53773500
H -2.66230500 -0.41941800 1.92694300
H -1.93556700 -0.32381700 -2.01668900
C -3.23422000 0.67149500 -0.58424600
H -3.90796400 1.02488700 -1.36971100
H -3.14501900 1.47437000 0.15730800
C -3.77757500 -0.59625600 0.07719100
H -3.96221600 -1.35985700 -0.68914500
H -4.73585700 -0.38529500 0.55829300
C 2.37263700 1.53623700 -0.12121200
H 2.78244400 2.54070300 -0.06160400
C 3.22428100 0.49496700 -0.28363000
H 4.29211500 0.70202500 -0.28380200

Energy = -561.420898 hartree

Imaginary frequency= -239.7850 cm-1

TS5 - transition state for the parent aniline molecule leading to indole.
H -4.22686200 0.66770800 -0.47438100
C -3.53392400 -0.11221600 -0.18123300
C -1.72426000 -2.17848800 0.49178600
C -2.22914300 0.19729700 0.24575600
C -3.88977000 -1.44203300 -0.29129500
S29
C -2.97996000 -2.47975000 0.01713100
C -1.32991100 -0.82284200 0.63111100
H -4.88294200 -1.69382000 -0.64817400
H -3.29140700 -3.51291000 -0.08945200
H -0.61401000 -0.58458700 1.41836500
H -1.04431600 -2.96363400 0.80509000
N -1.65972200 1.44502400 0.10039100
C -0.31606900 1.43509400 -0.12158200
C 0.29778500 0.20706200 -0.21561000
N 1.49581100 -0.21219100 0.03950900
C 2.33229200 0.29420200 1.14816300
H 1.84906000 1.18524800 1.55305800
H 2.34566500 -0.48129900 1.92671100
C 2.02827900 -1.41196100 -0.63263200
H 1.33491000 -1.67431000 -1.43228500
H 2.04080300 -2.22511300 0.10651300
C 3.74944100 0.57776100 0.65605000
H 3.72120200 1.41627800 -0.05041700
H 4.35719100 0.88999900 1.51003500
C 3.43844400 -1.14247400 -1.15087100
H 3.38699200 -0.38679400 -1.94406100
H 3.82724900 -2.06150500 -1.59821600
C 4.34926500 -0.65525500 -0.02272800
H 4.47341500 -1.45542800 0.71864400
H 5.34349700 -0.42240300 -0.41312000
C 0.41244300 2.69730200 -0.47899400
H 0.46301700 3.36000900 0.39118400
H -0.08300300 3.22980600 -1.29418600
H 1.42971400 2.45749900 -0.78961500
C -2.47740200 2.63822500 -0.12351000
H -3.38876600 2.55323100 0.46582800
H -2.72570000 2.74217300 -1.18375100
H -1.93339400 3.51846600 0.21368400

Energy = -692.941861 hartree

Imaginary frequency= -247.3606 cm-1

TS6 - transition state for the parent phenyl ether molecule leading to benzofuran.
H 4.21955600 1.19310600 0.65045900
C 3.61223200 0.37545400 0.28016700
C 1.94106100 -1.75556300 -0.57936600
C 2.32850600 0.61200100 -0.19785600
C 4.02983200 -0.94543400 0.33897000
C 3.19013400 -2.01024200 -0.06060100
C 1.48283500 -0.41029800 -0.67911600
H 5.01474800 -1.16829800 0.73580400
H 3.55128200 -3.02941600 0.01581900
H 0.86306700 -0.16578300 -1.54860900
S30
H 1.32244400 -2.55896700 -0.96432000
O 1.73712100 1.81681200 -0.01158500
C 0.39400400 1.69947700 0.13521900
C -0.32687500 2.94424100 0.51590800
H -0.33391800 3.63462100 -0.33260500
H 0.17699900 3.42832900 1.35538900
H -1.35584400 2.71057000 0.79106100
C -0.12376600 0.45577500 0.07818500
N -1.29128800 -0.09762800 -0.05855500
C -1.64253300 -1.30172700 0.71563400
H -1.54044900 -2.16679600 0.04462800
H -0.91915000 -1.39886400 1.52630100
C -2.19060900 0.21254700 -1.18873200
H -2.09970500 -0.60481000 -1.91851900
H -1.83816800 1.13662800 -1.65106300
C -3.07564600 -1.19331100 1.22914000
H -3.33013400 -2.12219300 1.74705400
H -3.12913900 -0.38075200 1.96326300
C -3.62994900 0.32918800 -0.69400200
H -4.27967800 0.49126400 -1.55864100
H -3.71371700 1.21177500 -0.04864900
C -4.04679900 -0.92373600 0.07860500
H -4.05744600 -1.78588400 -0.60087700
H -5.06326300 -0.80585800 0.46312900

Energy = -673.528589 hartree

Imaginary frequency= -328.9631 cm-1

TS7 - transition state for the parent phenyl sulfide molecule leading to benzothiophene.
H -4.61520800 -2.01902400 -0.77277500
C -3.70769700 -1.59386600 -0.35691300
C -1.35783400 -0.52130500 0.69920200
C -2.67565700 -2.45302700 0.07459100
C -3.57387300 -0.21402800 -0.29849400
C -2.38398400 0.31698900 0.20371200
C -1.52116100 -1.93096300 0.61635800
H -2.80973400 -3.52663300 0.00569500
H -4.34772000 0.43809500 -0.68935900
H -0.75582000 -2.58251800 1.02564000
H -0.78377100 -0.14105100 1.55016300
C 0.22469600 0.46754300 -0.04641300
C -0.25788500 1.71961300 -0.15438400
S -1.96237800 1.98826400 0.00968400
N 1.37423900 -0.11774400 0.10015800
C 2.31307600 0.22795600 1.18781700
H 2.24588800 -0.56459300 1.94631400
H 1.97872000 1.16735900 1.63137100
C 1.69417000 -1.34786000 -0.64604800
S31
H 1.62425000 -2.19034700 0.05657400
H 0.93877800 -1.47312500 -1.42328700
C 3.73423800 0.32287500 0.63694300
H 4.41522700 0.50846100 1.47227900
H 3.79863600 1.18477200 -0.03788400
C 3.10635300 -1.25469900 -1.21816800
H 3.13129500 -0.46332300 -1.97661000
H 3.34053400 -2.19844900 -1.71839200
C 4.11944000 -0.95404300 -0.11233400
H 4.15266500 -1.79586700 0.59133500
H 5.12142100 -0.85106100 -0.53692400
C 0.60097500 2.88129700 -0.57724500
H 0.11395200 3.45776300 -1.36663600
H 1.56410100 2.52091900 -0.94260300
H 0.77602200 3.54170400 0.27731600

Energy = -675.695404 hartree

Imaginary frequency= -347.6698 cm-1

TS8 - transition state for the parent styrene molecule leading to naphthalene.
C -2.58360900 0.40718300 0.15661200
C -1.50962400 -0.27591200 0.78379900
H -1.02690200 0.23678600 1.61975000
C -0.07581000 1.93601900 -0.13169300
C 0.20603300 0.62655300 0.02952300
C 1.00798100 2.81366500 -0.72467300
H 1.36967800 3.50231400 0.04634000
H 0.60572700 3.40630200 -1.54913400
H 1.85081400 2.22689400 -1.09117500
N 1.24072200 -0.12071100 0.22409900
C 1.41138500 -1.41135600 -0.46943800
H 0.56748700 -1.54375600 -1.14780100
H 1.39406700 -2.20659900 0.28660800
C 2.30814000 0.22067900 1.19399500
H 2.07643600 1.20132500 1.61255600
C 2.75282700 -1.41432800 -1.20045400
H 2.87858200 -2.38656400 -1.68485400
H 2.73158100 -0.65199400 -1.98859100
H 2.26500800 -0.52590200 1.99714900
C 3.67145300 0.19053100 0.50492100
H 4.44032800 0.35520500 1.26508800
H 3.73455900 1.02155600 -0.20699300
C 3.89592500 -1.13592900 -0.22316100
H 3.95402000 -1.95162500 0.50902300
H 4.85067000 -1.11274200 -0.75488400
C -1.37974600 2.53023000 0.04378600
S32
H -1.41761100 3.61031000 -0.06415500
C -2.54995200 1.84138600 0.11062900
H -3.48445800 2.38348100 -0.00342100
C -3.60236400 -0.33594500 -0.47219100
H -4.42547000 0.18519300 -0.95089000
C -3.53152900 -1.71541100 -0.50019200
H -4.30709900 -2.28331400 -1.00348400
C -1.48405900 -1.69634400 0.78435500
H -0.70397200 -2.21794200 1.32910100
C -2.46835600 -2.40080700 0.12911700
H -2.45065400 -3.48524100 0.12146100

Energy = -996.537849 hartree

Imaginary frequency= -278.4581 cm-1

Cartesian coordinates for intermediates (Int)

Pyrrole 9
H 3.96161000 -1.52343300 1.22752900
C 3.52256300 -1.72423900 0.24637600
H 4.27972000 -1.51652700 -0.51640800
H 3.26247700 -2.78099700 0.18997300
C 2.30460000 -0.90177300 0.02056600
C 0.94862900 -1.41682100 -0.29769400
H 0.62462600 -2.08446500 0.51173600
H 0.96251000 -2.00957900 -1.21988000
C 0.90478000 0.90509700 -0.12959300
C 0.10756600 -0.16996400 -0.41861500
C 0.69420200 2.38525000 -0.03709200
H -0.33310400 2.61515500 0.24015900
H 0.91880700 2.90247500 -0.97652800
H 1.32463300 2.81756100 0.74325100
N -1.18124900 -0.25240900 -0.85849600
C -2.03426300 0.93535000 -0.91204200
H -1.44906100 1.78679000 -1.25894900
H -2.79618200 0.74144200 -1.67623400
C -1.96434700 -1.45803700 -0.55874000
H -1.32758600 -2.34212800 -0.61283600
H -2.71718700 -1.55659500 -1.34915900
C -2.64925300 -1.32576500 0.80465600
H -1.87922900 -1.27245900 1.58650400
H -3.25276000 -2.21756800 1.00074200
C -2.71380500 1.17672400 0.43801400
H -1.94860100 1.38298000 1.19866200
H -3.36150500 2.05691600 0.37564500
C -3.51855200 -0.06347900 0.84543100
S33
H -3.94588200 0.07097500 1.84332200
H -4.36023700 -0.18677800 0.15092200
N 2.23167200 0.39214000 0.09796400
C 3.36033200 1.27060800 0.40423400
H 3.37809800 2.08782200 -0.31626100
H 3.24594800 1.66908900 1.41362100
H 4.28523300 0.70350200 0.33491000

Energy = -578.733434 hartree

Furan 10
H -4.33202200 -1.52483900 0.54091500
C -3.95087300 -1.06583500 -0.37742800
H -3.86144200 -1.86288200 -1.12201300
H -4.63760700 -0.29580500 -0.72495600
C -2.62072800 -0.49633000 -0.11427100
C -1.37173900 -1.17337100 0.29514800
H -1.11353500 -1.92965800 -0.45851800
H -1.51382400 -1.70590600 1.24386700
C -1.05480000 1.10694400 0.02471900
C -0.39425300 -0.02553500 0.39197700
C -0.80023600 2.56653300 -0.12427900
H 0.19143100 2.75240500 -0.53898000
H -0.89028500 3.10427300 0.82453600
H -1.53091100 2.98216900 -0.82129600
N 0.86463200 -0.20466100 0.87715100
C 1.53868800 -1.49260500 0.66554100
H 0.81959900 -2.30807100 0.75997800
H 2.26490700 -1.60975600 1.47758600
C 1.81061500 0.91452200 0.85732700
H 1.28576700 1.83387000 1.11959800
C 2.25398300 -1.51051000 -0.68824100
H 2.78274700 -2.46099700 -0.80916500
H 1.50629900 -1.44833200 -1.49053700
H 2.54172400 0.72481600 1.65137800
C 2.52315700 0.99735200 -0.49404400
H 3.24048100 1.82375600 -0.48159100
H 1.78684600 1.21301300 -1.28041000
C 3.22708100 -0.33085200 -0.79587700
H 4.04332100 -0.47384800 -0.07555600
H 3.68071700 -0.30416400 -1.79068600
O -2.41025100 0.74758800 -0.25095600

Energy = -559.307366 hartree

Thiophene 11
H -3.81192900 -2.25573000 0.67276100
C -3.62880900 -1.70893300 -0.25784800
S34
H -3.38489200 -2.44690600 -1.02900200
H -4.53794800 -1.18006000 -0.54470400
C -2.48463500 -0.77788700 -0.07714400
C -1.10567200 -1.19489900 0.29216400
H -0.74078000 -1.89925600 -0.46936700
H -1.13234600 -1.75135100 1.23862000
S -2.55272400 0.83255400 -0.27457100
C -0.90500600 1.19800400 0.07481800
C -0.22166000 0.03006900 0.38868600
C -0.51448000 2.65217000 -0.00213600
H -0.27856400 3.06831800 0.98099500
H -1.34445200 3.23642900 -0.40686200
H 0.33842400 2.80975800 -0.66719300
N 1.05809100 -0.12114100 0.78368100
C 1.71897600 -1.43374600 0.75613600
H 0.99743500 -2.23251700 0.92124600
H 2.42022700 -1.45561000 1.59761800
C 2.04344200 0.96496300 0.72762700
H 1.55571600 1.92179300 0.88628300
C 2.47544400 -1.60399500 -0.56488800
H 2.98295300 -2.57332100 -0.56931300
H 1.75305500 -1.60776300 -1.39190600
H 2.73140100 0.81089600 1.56650800
C 2.80814000 0.90416000 -0.59602200
H 3.55060400 1.70742500 -0.62446400
H 2.10411800 1.07592100 -1.42129300
C 3.48096600 -0.46334200 -0.75631000
H 4.27612600 -0.55967400 -0.00552500
H 3.95755000 -0.54061000 -1.73752800

Energy = -882.318104 hartree

Benzene 12
H -3.36005800 -2.67961300 0.78642300
C -3.28393600 -2.24332900 -0.21528400
H -2.75020400 -2.96600200 -0.84166000
H -4.28986000 -2.10871400 -0.61486900
C -2.54702900 -0.94227300 -0.16684800
C -1.18102900 -0.97492600 0.45233400
H -0.62794600 -1.81916700 0.02841400
H -1.31513700 -1.21416100 1.52100800
C -1.03417000 1.53162000 0.08477100
C -0.34800500 0.27764500 0.33984000
C -0.47345100 2.89299400 0.43813200
H 0.22369700 2.83669800 1.27724500
H -1.29934500 3.53988300 0.73936900
S35
H 0.03214400 3.38139900 -0.39958700
N 0.95180800 0.17034300 0.51771500
C 1.59364000 -1.04487600 1.06332100
H 0.84987200 -1.68593800 1.52820800
H 2.26058500 -0.69156900 1.85795400
C 1.95932300 1.14039400 0.03670200
H 1.46764800 2.01426700 -0.37015500
C 2.40609000 -1.76334700 -0.01265300
H 2.86662700 -2.64866900 0.43407800
H 1.73552400 -2.10677400 -0.81006200
H 2.57631600 1.43911500 0.89056000
C 2.80491100 0.47759500 -1.05701100
H 3.55568300 1.20444900 -1.38012200
H 2.15610900 0.27280000 -1.91723500
C 3.46201600 -0.81527500 -0.57973100
H 4.19982900 -0.58727400 0.19988900
H 3.99978000 -1.29078600 -1.40406900
C -2.31601900 1.44639800 -0.37707900
H -2.84237700 2.38114900 -0.55739200
C -3.05202200 0.22645600 -0.59926100
H -4.04344500 0.28205400 -1.03541200

Energy = -561.490982 hartree

Indole 13
H -4.41782200 0.21121100 0.09970800
C -3.53658600 -0.41780000 0.13231500
C -1.21499300 -2.14168300 0.09242000
C -2.23057700 0.13852400 0.18163000
C -3.63003400 -1.77456300 0.02788800
C -2.46747800 -2.63303100 -0.02195200
C -1.02109000 -0.69277600 0.36048100
H -4.61106200 -2.23145000 -0.04873500
H -2.61895300 -3.69975400 -0.14267600
H -0.84067800 -0.65094000 1.46315800
H -0.35709500 -2.80245300 0.11762000
N -1.85189700 1.38992400 -0.02409200
C -0.45551400 1.49491300 -0.16866800
C 0.11152300 0.25958100 -0.03649900
N 1.45284600 -0.01031100 -0.02978500
C 2.30309400 0.63728400 0.98083400
H 1.89039300 1.62159500 1.20924400
H 2.27077100 0.03795400 1.90805500
C 1.90758700 -1.34819700 -0.41099100
H 1.23667400 -1.73520800 -1.18137200
S36
H 1.87527800 -2.02584100 0.46078900
C 3.74054400 0.74276200 0.48491200
H 3.76970100 1.42117500 -0.37683300
H 4.35892200 1.18124900 1.27399500
C 3.33756200 -1.28240700 -0.94382300
H 3.33979400 -0.69857100 -1.87192700
H 3.67138800 -2.29553200 -1.18781100
C 4.27089600 -0.63327200 0.07884400
H 4.33601100 -1.27324400 0.96918600
H 5.28210800 -0.54796100 -0.32911300
C 0.20172900 2.79418300 -0.48391800
H 0.28914200 3.44116600 0.39577400
H -0.34623000 3.33911800 -1.25712100
H 1.20628100 2.59090400 -0.86153700
C -2.75329700 2.52768000 -0.19896200
H -2.31331000 3.40274800 0.27724600
H -2.90115400 2.72051400 -1.26357300
H -3.70699500 2.30884800 0.27600100

Energy = -692.966902 hartree

Benzofuran 14
H -4.44802800 1.04905700 -0.06853900
C -3.69127300 0.28168500 0.03864900
C -1.65193000 -1.77380300 0.16663100
C -2.33696600 0.61061000 0.11993500
C -3.97809700 -1.06403500 -0.00643600
C -2.96678000 -2.08277700 0.03981100
C -1.26501300 -0.35885100 0.34523400
H -5.01306200 -1.37389500 -0.10948300
H -3.27433600 -3.12008700 -0.02187800
H -1.11869700 -0.29715700 1.45613300
H -0.89812700 -2.54575500 0.26528300
O -1.83955900 1.80092100 -0.09376500
C -0.45217300 1.72027500 -0.22328600
C 0.25366500 2.98267600 -0.53819500
H 0.37392300 3.61103000 0.34967600
H -0.30221500 3.54755900 -1.29018200
H 1.24285200 2.74194100 -0.93409200
C -0.02074000 0.44468500 -0.06766100
N 1.28072400 0.02282400 -0.05504300
C 1.56467200 -1.36716300 -0.41781100
H 1.43362700 -2.02330100 0.46151300
H 0.85902600 -1.67387200 -1.19406700
C 2.18918000 0.57026600 0.96524000
H 2.06572900 -0.00306800 1.90071000
H 1.90477300 1.60475000 1.16809900
C 2.99858500 -1.49169300 -0.92755600
S37
H 3.20311700 -2.54205400 -1.15569500
H 3.09003900 -0.92408400 -1.86104200
C 3.63481700 0.48176600 0.49016900
H 4.29302100 0.84645100 1.28441300
H 3.76257400 1.14089700 -0.37724700
C 3.99009500 -0.95559800 0.10602200
H 3.95874600 -1.58940400 1.00258500
H 5.01019500 -1.00439700 -0.28524800

Energy = -673.542962 hartree

Benzothiophene 15
H -4.78216100 -1.91760800 -0.26897600
C -3.79903700 -1.48875800 -0.10530000
C -1.21227600 -0.44122700 0.40094000
C -2.68959100 -2.37423400 0.10214300
C -3.65507300 -0.12269800 -0.12306400
C -2.36356000 0.40651300 0.04631400
C -1.43773000 -1.89935900 0.31525800
H -2.86771200 -3.44348400 0.09883900
H -4.49553400 0.53189300 -0.32455400
H -0.61815500 -2.57024000 0.54267500
H -1.14648200 -0.28171900 1.50954700
C 0.07860000 0.33775300 0.10260100
C -0.19681300 1.66566300 -0.10338100
S -1.89448900 1.99770200 -0.18298100
N 1.31628900 -0.20379600 0.22553200
C 2.34178300 0.36525600 1.10665300
H 2.42908800 -0.28938400 1.98860000
H 2.00406100 1.34212100 1.45559500
C 1.64409500 -1.51672500 -0.33306400
H 1.72341600 -2.25897600 0.47730600
H 0.84640000 -1.81911700 -1.01425500
C 3.69396300 0.44951300 0.40363100
H 4.44494800 0.79866700 1.11871400
H 3.63783500 1.18942500 -0.40431300
C 2.97459200 -1.44400900 -1.08366700
H 2.85431100 -0.78304000 -1.95058500
H 3.22248100 -2.44197600 -1.45792000
C 4.08317700 -0.91281700 -0.17381200
H 4.24906700 -1.62260300 0.64783600
H 5.02407000 -0.83686700 -0.72603900
C 0.78089400 2.76496700 -0.38199400
H 0.35852100 3.49926200 -1.07159100
H 1.67619100 2.33713300 -0.84157300
H 1.07932500 3.29083300 0.53011900

Energy = -996.556867 hartree

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Naphthalene 16

C 2.48899700 0.48378300 -0.32973400

C 1.21593900 -0.29996700 -0.17890900
H 1.09128200 -0.70430700 -1.20843100
C -0.00038100 1.92068300 0.08926900
C -0.05509600 0.47901100 0.09782400
C -1.20249400 2.83527600 0.16498400
H -2.05629900 2.43100000 -0.38064000
H -0.94446700 3.78926400 -0.29662100
H -1.51407800 3.04878100 1.19087400
N -1.16758700 -0.22443300 0.28547000
C -2.35213500 0.23174900 1.04678600
H -2.14251700 1.18787500 1.51064800
H -2.45659100 -0.49894200 1.85894300
C -1.37401600 -1.59540900 -0.23676900
H -0.50032200 -1.93049800 -0.78846800
C -3.62447800 0.23276300 0.20444200
H -4.45971100 0.52499700 0.84717600
H -3.54601200 0.98169800 -0.59138000
H -1.52575700 -2.27091700 0.61335800
C -2.60394000 -1.60715700 -1.14851800
H -2.72340200 -2.62553600 -1.52938500
H -2.41103000 -0.95519000 -2.00895600
C -3.85723000 -1.14802900 -0.40723300
H -4.09429400 -1.86594100 0.38804600
H -4.71312900 -1.12486400 -1.08658100
C 1.21641400 2.51033400 -0.16746400
H 1.22742100 3.59434300 -0.24729100
C 2.45469000 1.83683800 -0.37327300
H 3.35366200 2.41312000 -0.56366200
C 3.70603200 -0.29257100 -0.46542800
H 4.58485000 0.19461400 -0.87602800
C 3.76321600 -1.55142700 0.02372400
H 4.68606700 -2.11900500 -0.03001400
C 1.42677000 -1.51539200 0.70842700
H 0.59050800 -1.90451300 1.27648000
C 2.62412900 -2.11730100 0.73740200
H 2.76842500 -3.01406800 1.33045600

Energy = -675.716234 hartree

S39
Characterization of Compounds 11a, 13a, 14a and 15a - 1H and 13C NMR Spectra
Compound 11a(2)

1.5

2.28
2.28
2.39
2.39
1.0

2.81
2.81
0.5

2.79
2.79
2.82
2.82
6.56
6.56

0
0.96

4.14

2.99
3.00

4.08
2.11
9 8 7 6 5 4 3 2 Chemical Shift (ppm)

1.4

1.3

1.2
54.26
54.26

1.1

1.0
76.84

0.9
76.84

26.68
26.68
77.16
77.16
77.48
77.48

0.8
119.28
119.28

0.7
24.42
24.42

0.6
15.82
15.82
12.38
12.38

0.5

0.4

0.3
134.05
134.05

122.27
122.27

0.2
148.71
148.71

0.1

200 180 160 140 120 100 80 60 40 20 Chemical Shift (ppm)

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 0
0

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
0.5
1.0

180
Compound 13a(3)

8
7.79
7.79
1.00

160
7.77
7.77
7.30
7.30
1.03 7.28
7.28
0.98 7.15
7.15

7
0.95 7.13
7.13

140
135.14
135.14 7.08
7.08
130.87
130.87 7.07
7.07
126.76
126.76 7.06
7.06
124.52
124.52 119.99
119.99

6
119.30
119.30

120
118.15
118.15
108.77
108.77

100
5

S41
77.36
77.36

80
76.72
76.72

4
3.05 3.66
3.66

60
3.21
3.21
54.48
54.48 4.03 3.20
3.20

3
3.19
3.19

40
3.03 2.41
2.41
29.46
29.46 1.78
1.78
27.37
27.37 1.76

2
24.60
24.60 1.75
4.01

20
1.74
1.74
2.03 1.72
1.72
9.58
9.58 1.66
1.66
1.64
1.64
1.63
1.63

Chemical Shift (ppm)

Chemical Shift (ppm)
 0

0
0.5
1.0

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2

200
9
Compound 14a(3)

180
7.63
7.63
7.61
7.61

8
7.36
7.36
1.02 7.34
7.34

160
7.28
7.28
153.05
153.05 0.94 7.19
7.19
2.00 7.17
7.17

7
146.32
146.32 7.17
7.17
7.16
7.16

140
7.16
7.16
129.47
129.47
126.98
126.98 122.79
122.79

6
121.69
121.69

120
119.66
119.66
111.01
111.01

100

S42
80
77.35
77.35

4
77.03
77.03
76.71
76.71

60
3.15
3.15
4.07 3.14
3.14

3
53.56
53.56
3.13
3.13

40
3.00 2.46
2.46
1.76

2
1.75
1.75
26.88
26.88 1.74
1.74
24.40
24.40 4.14
1.72

20
2.03 1.71
1.711.72
1.62
12.38
12.38 1.61
1.61
1.59
1.59
Chemical Shift (ppm)

Chemical Shift (ppm)

 0

0
0.5
1.0

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4

200
9
7.82
7.82
Compound 15a(4)

180
7.80
7.80
7.73
7.73

8
0.99 7.71
7.71
0.92 7.36
7.36
7.34
7.34
1.01

160
7.31
7.31
1.01 7.30
7.30

7
7.29
7.29
7.28
7.28
141.77
141.77
138.31
138.31

140
136.49
136.49

6
129.30
129.30
123.53
123.53
123.39
123.39

120
122.41
122.41
121.72
121.72

100

S43
4
77.42
77.42
77.10
77.10

80
76.78
76.78
3.27
3.27
3.94 3.26
3.26
3.25
3.25

60
3.00 2.59
52.45
52.45
1.81
1.81
1.80
1.80

2
1.79
1.79

40
4.04 1.77
1.77
2.03 1.76
1.76
1.70
1.70
27.40
27.40 1.70
1.70
24.68
24.68
1.68
1.68

14.20
14.20
Chemical Shift (ppm)

Chemical Shift (ppm)

References
(1) Hoffmann, R.; Woodward, R. B. The Conservation of Orbital Symmetry. Acc. Chem. Res. 1968, 1
(1), 17–22.
(2) Dagoneau, D.; Kolleth, A.; Lumbroso, A.; Tanriver, G.; Catak, S.; Sulzer‐Mossé, S.; De
Mesmaeker, A. Straightforward Synthesis of 3‐Aminothiophenes Using Activated Amides. Helv.
Chim. Acta 2019, 102 (4), e1900031.
(3) Dagoneau, D.; Kolleth, A.; Quinodoz, P.; Tanriver, G.; Catak, S.; Lumbroso, A.; Sulzer-Mossé, S.;
De Mesmaeker, A. Keteniminium Salts as Key Intermediate for the Efficient Synthesis of 3-
Amino-Indoles and -Benzofurans. Helv. Chim. Acta 2019, 102, No. e1900217.
(4) Lumbroso, A.; Behra, J.; Kolleth, A.; Dakas, P. Y.; Karadeniz, U.; Catak, S.; Sulzer-Mossé, S.; De
Mesmaeker, A. Access to Functionalized 3-Amino-Benzothiophenes Using Keteniminium
Intermediates. Tetrahedron Lett. 2015, 56 (47), 6541–6545.

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